Polyamide-imide film and method for producing same

ABSTRACT

An embodiment can provide a polyamide-imide film and a method for producing same, the film comprising a polyamide-imide polymer formed by polymerizing an aromatic diamine compound, an aromatic dianhydride compound and a dicarbonyl compound, wherein, in an XRD graph with a section in which 2θ=8° to 32° as a baseline, the film shows a peak area of 50% or above around 2θ=23° with respect to a peak area seen around 2θ=15°.

TECHNICAL FIELD

Embodiments relate to a polyamide-imide film having specific XRDcharacteristics and being colorless, transparent, and excellent inmechanical properties and optical properties, and a process forpreparing the same.

BACKGROUND ART

Since polyamide-imide (PAI) is excellent in resistance to friction,heat, and chemicals, it is employed in such applications as primaryelectrical insulation, coatings, adhesives, resins for extrusion,heat-resistant paintings, heat-resistant boards, heat-resistantadhesives, heat-resistant fibers, and heat-resistant films.

Polyamide-imide is used in various fields. For example, polyamide-imideis made in the form of a powder and used as a coating for a metal or amagnetic wire. It is mixed with other additives depending on theapplication thereof. In addition, polyamide-imide is used together witha fluoropolymer as a painter for decoration and corrosion prevention. Italso plays a role of bonding a fluoropolymer to a metal substrate.Further, polyamide-imide is used to coat kitchenware, used as a membranefor gas separation by virtue of its heat resistance and chemicalresistance, and used in natural gas wells for filtration of suchcontaminants as carbon dioxide, hydrogen sulfide, and impurities.

In recent years, polyamide-imide has been developed in the form of afilm, which is less expensive and has excellent optical, mechanical, andthermal characteristics.

DISCLOSURE OF INVENTION Technical Problem

Embodiments aim to provide a polyamide-imide film having specific XRDcharacteristics and being colorless, transparent, and excellent inmechanical properties and optical properties, and a process forproducing the same.

Solution to Problem

According to an embodiment, there is provided a polyamide-imide film,which comprises a polyamide-imide polymer formed by polymerizing anaromatic diamine compound, an aromatic dianhydride compound, and adicarbonyl compound, wherein the peak area in the vicinity of 2θ=23° is50% or more based on the peak area in the vicinity of 2θ=15° when a baseline is taken in the region between 2θ=8° and 32° in an XRD graph of thepolyamide-imide film.

According to another embodiment, there is provided a process forproducing a polyamide-imide film, which comprises polymerizing anaromatic diamine compound, an aromatic dianhydride compound, and adicarbonyl compound to prepare a polyamide-imide polymer solution;charging the polymer solution into a tank; extruding and casting thepolymer solution in the tank and then drying the cast polymer solutionto prepare a gel sheet; and thermally treating the gel sheet, whereinthe viscosity of the polymer solution is 100,000 to 300,000 cps, thethermal treatment is carried out in a temperature range of 80 to 500° C.at a temperature elevation rate of 2° C./min to 80° C./min for 5 to 40minutes, and the maximum temperature in the thermal treatment is 300 to500° C.

Advantageous Effects of Invention

The polyamide-imide film according to the embodiment has specific XRDcharacteristics and is colorless, transparent, and excellent inmechanical properties and optical properties.

The process for producing a polyamide-imide film according to theembodiment is capable of providing a polyamide-imide film havingspecific XRD characteristics and being colorless, transparent, andexcellent in mechanical properties and optical properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an XRD graph of the film produced in Example 1.

FIG. 2 is an XRD graph of the film produced in Example 2.

FIG. 3 is an XRD graph of the film produced in Example 3.

FIG. 4 is an XRD graph of the film produced in Comparative Example 1.

FIG. 5 is an XRD graph of the film produced in Comparative Example 2.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail withreference to the examples. The examples may be modified into variousforms as long as the gist of the invention is not altered.

In this specification, when a part is referred to as “comprising” anelement, it is to be understood that the part may comprise otherelements as well, unless otherwise indicated.

Further, all numbers and expression related to the quantities ofcomponents, reaction conditions, and the like used herein are to beunderstood as being modified by the term “about,” unless otherwiseindicated.

The terms first, second, and the like are used herein to describevarious elements, and the elements should not be limited by the terms.The terms are used only for the purpose of distinguishing one elementfrom another.

[Polyamide-Imide Film]

An Embodiment provides a polyamide-imide film having specific XRDcharacteristics and being colorless, transparent, and excellent inmechanical properties and optical properties.

The polyamide-imide film according to the embodiment comprises apolyamide-imide polymer formed by polymerizing an aromatic diaminecompound, an aromatic dianhydride compound, and a dicarbonyl compound.

The molar ratio of the aromatic diamine compound to the aromaticdianhydride compound may be 10:2 to 10:4, specifically 10:2 to 10:3. Ifthe above molar ratio range is satisfied, it is possible to provide apolyamide-imide film that is excellent in mechanical properties andoptical properties.

The polyamide-imide polymer comprises an imide repeat unit derived fromthe polymerization of the aromatic diamine compound and the aromaticdianhydride compound and amide repeat units derived from thepolymerization of the aromatic diamine compound and the dicarbonylcompound.

The aromatic diamine compound is a compound that forms an imide bondwith the aromatic dianhydride compound and forms amide bonds with thedicarbonyl compound, to thereby form a copolymer.

In an embodiment, one kind of aromatic diamine may be used as thearomatic diamine compound. If a single kind of aromatic diamine compoundis used, the chemical structure of the polyamide-imide polymer can beeasily designed, and the process efficiency can be enhanced.

For example, the aromatic diamine compound may comprise2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB) represented by thefollowing Formula 1, but it is not limited thereto.

The aromatic dianhydride compound is a compound that can contribute toimprovements in the optical properties such as transmittance of thepolyamide-imide film, since it has a low birefringence value.

In an embodiment, one kind of aromatic dianhydride may be used as thearomatic diamine compound. If a single kind of aromatic diamine compoundis used, the chemical structure of the polyamide-imide polymer can beeasily designed, and the process efficiency can be enhanced.

The aromatic dianhydride compound may comprise a compound having afluorine-containing substituent. Or the aromatic dianhydride compoundmay be composed of a compound having a fluorine-containing substituent.In such event, the fluorine-containing substituent may be a fluorinatedhydrocarbon group and specifically may be a trifluoromethyl group. Butit is not limited thereto.

For example, the aromatic dianhydride compound may comprise2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA)represented by the following Formula 2, but it is not limited thereto.

The aromatic diamine compound and the dianhydride compound may bepolymerized to form a polyamic acid.

Subsequently, the polyamic acid may be converted to a polyimide througha dehydration reaction, and the polyimide comprises an imide repeatunit.

For example, the polyimide may comprise a compound represented by thefollowing Formula 3, but it is not limited thereto.

In the above Formula 3, n is an integer of 1 to 400.

The dicarbonyl compound may comprise at least two dicarbonyl compoundsdifferent from each other.

For example, the dicarbonyl compound may comprise a first dicarbonylcompound and/or a second dicarbonyl compound.

The first dicarbonyl compound and the second dicarbonyl compound may bean aromatic dicarbonyl compound, respectively.

The first dicarbonyl compound and the second dicarbonyl compound may becompounds different from each other.

For example, the first dicarbonyl compound and the second dicarbonylcompound may be aromatic dicarbonyl compounds different from each other,but they are not limited thereto.

If the first dicarbonyl compound and the second dicarbonyl compound arean aromatic dicarbonyl compound, respectively, they comprise a benzenering. Thus, they can contribute to improvements in the mechanicalproperties such as surface hardness and tensile strength of thepolyamide-imide film thus produced.

In an embodiment, two kinds of aromatic dicarbonyl compound may be usedas the dicarbonyl compound. If two kinds of aromatic dicarbonyl compoundare used, the chemical structure of the polyamide-imide polymer can bedesigned to materialize the desired properties, and the processefficiency can be enhanced.

The dicarbonyl compound may comprise terephthaloyl chloride (TPC),1,1′-biphenyl-4,4′-dicarbonyl dichloride (BPDC), or a combinationthereof. But it is not limited thereto.

For example, the first dicarbonyl compound may comprise1,1′-biphenyl-4,4′-dicarbonyl dichloride (BPDC) represented by thefollowing Formula 4, but it is not limited thereto.

Further, the second dicarbonyl compound may comprise terephthaloylchloride (TPC) represented by the following Formula 5, but it is notlimited thereto.

If 1,1′-biphenyl-4,4′-dicarbonyl dichloride (BPDC) is used as the firstdicarbonyl compound and terephthaloyl chloride (TPC) is used as thesecond dicarbonyl compound in a proper combination, the polyamide-imidefilm thus produced may have high oxidation resistance.

In addition, the aromatic diamine compound and the dicarbonyl compoundmay be polymerized to form amide repeat units represented by thefollowing Formulae 6 and 7.

In the above Formula 6, x is an integer of 1 to 400.

In the above Formula 7, y is an integer of 1 to 400.

The polyamide-imide film according to another embodiment may comprise apolyamide-imide polymer formed by polymerizing an aromatic diaminecompound, an aromatic dianhydride compound, and a dicarbonyl compound,wherein the aromatic diamine compound may comprise one kind of aromaticdiamine compound, the aromatic dianhydride compound may comprise onekind of aromatic dianhydride compound, and the dicarbonyl compound maycomprise two kinds of aromatic dicarbonyl compound.

For example, the aromatic diamine compound may comprise2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB), the aromaticdianhydride compound may comprise 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6-FDA), and the dicarbonyl compound maycomprise terephthaloyl chloride (TPC), 1,1′-biphenyl-4,4′-dicarbonyldichloride (BPDC), or a combination thereof. But they are not limitedthereto.

Alternatively, the aromatic diamine compound may be composed of one kindof diamine compound, the aromatic dianhydride compound may be composedof one kind of aromatic dianhydride compound, and the dicarbonylcompound may be composed of two kinds of dicarbonyl compound.

For example, the aromatic diamine compound may be composed of2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB), the aromaticdianhydride compound may be composed of 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6-FDA), and the dicarbonyl compound maybe composed of terephthaloyl chloride (TPC) and1,1′-biphenyl-4,4′-dicarbonyl dichloride (BPDC).

An embodiment is characterized in that it is capable of providing apolyamide-imide film whose optical characteristics, mechanicalproperties, and flexibility are improved in a well-balanced mannerwithout a complicated process by properly controlling the content of theimide repeat unit and those of the amide repeat units.

Further, it is possible to provide a polyamide-imide film whose opticalcharacteristics, mechanical properties, and flexibility are improved ina well-balanced manner without such steps as precipitation, filtration,drying, and redissolution as adopted in the prior art.

The content of the imide repeat unit and those of the amide repeat unitsmay be controlled by the amounts of the aromatic dianhydride compoundand the dicarbonyl compound.

In the polyamide-imide polymer contained in the polyamide-imide film,the molar ratio of the imide repeat unit to the amide repeat units maybe 50:50 to 20:80, but it is not limited thereto.

If the molar ratio of the imide repeat unit to the amide repeat units iswithin the above range, the polyamide-imide film is excellent in suchoptical properties as transmittance and haze.

In an XRD graph of the polyamide-imide film, the peak area in thevicinity of 2θ=23° is 50% or more based on the peak area in the vicinityof 2θ=15° when a base line is taken in the region between 2θ=8° and 32°.Specifically, the peak area in the vicinity of 2θ=23° may be 55% ormore, 60% or more, 65% or more, 70% or more, or 75% or more, based onthe peak area in the vicinity of 2θ=15° when a base line is taken in theregion between 2θ=8° and 32°, but it is not limited thereto. Morespecifically, the peak area in the vicinity of 2θ=23° may be 50% to 98%,55% to 98%, 60% to 98%, 65% to 98%, 70% to 98%, 75% to 98%, 50% to 95%,55% to 95%, 60% 95%, 65% to 95%, 70% to 95%, 75% to 95%, 50% to 90%, 55%to 90%, 60% to 90%, 65% to 90%, 70% to 90%, 75% to 90%, or 75% to 85%,based on the peak area in the vicinity of 2θ=15° when a base line istaken in the region between 2θ=8° and 32°, but it is not limitedthereto.

The vicinity of 2θ=15° refers to 2θ=15°+1°, and the vicinity of 2θ=23°refers to 2θ=23°+1°.

The polyamide-imide film has a modulus of 5.0 GPa or more based on athickness of 50 μm. Specifically, the modulus may be 5.2 GPa or more,5.3 GPa or more, 5.4 GPa, or 5.5 GPa or more, but it is not limitedthereto.

The polyamide-imide film has a surface hardness of HB or higher.Specifically, the surface hardness may be H or higher or 2H or higher,but it is not limited thereto.

The polyamide-imide film has a yellow index (YI) of 5 or less based on athickness of 50 μm. Specifically, the yellow index may be 4.5 or less,but it is not limited thereto. More specifically, the yellow index maybe 4.4 or less, 4.3 or less, 4.1 or less, 4.0 or less, 3.9 or less, 3.8or less, or 3.6 or less, but it is not limited thereto.

The polyamide-imide film has a haze of 2% or less based on a thicknessof 50 μm. Specifically, the haze may be 1.8% or less or 1.5% or less,but it is not limited thereto. More specifically, the haze may be 1.0%or less or 0.9% or less, but it is not limited thereto.

The polyamide-imide film has a light transmittance measured at 550 nm of85% or more based on a thickness of 50 μm. Specifically, the lighttransmittance measured at 550 nm based on a thickness of 50 μm may be88% or more or 89% or more, but it is not limited thereto.

The polyamide-imide film has a tensile strength of 15 kgf/mm² or morebased on a thickness of 50 μm. Specifically, the tensile strength may be18 kgf/mm² or more, but it is not limited thereto.

The polyamide-imide film has an elongation of 15% or more based on athickness of 50 μm. Specifically, the elongation may be 16% or more, butit is not limited thereto.

The various characteristics of the polyamide-imide film described abovemay be combined.

For example, the polyamide-imide film may comprise a polyamide-imidepolymer formed by polymerizing an aromatic diamine compound, an aromaticdianhydride compound, and a dicarbonyl compound, wherein the peak areain the vicinity of 2θ=23° may be 50% or more based on the peak area inthe vicinity of 2θ=15° when a base line is taken in the region between2θ=8° and 32° in an XRD graph of the polyamide-imide film.

As another example, the peak area in the vicinity of 2θ=23° may be 50%or more based on the peak area in the vicinity of 2θ=15° when a baseline is taken in the region between 2θ=8° and 32° in an XRD graph of thepolyamide-imide film, and the polyamide-imide film may have a modulus of5.0 GPa or more, a surface hardness of HB or higher, a yellow index of 5or less, a haze of 2% less, a light transmittance measured at 550 nm of85% or more, based on a thickness of 50 μm.

As another example, the polyamide-imide film may comprise apolyamide-imide polymer formed by polymerizing an aromatic diaminecompound, an aromatic dianhydride compound, and a dicarbonyl compound,wherein the aromatic diamine compound may comprise2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB), the aromaticdianhydride compound may comprise 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6-FDA), and the dicarbonyl compound maycomprise terephthaloyl chloride (TPC), 1,1′-biphenyl-4,4′-dicarbonyldichloride (BPDC), or a combination thereof.

[Process for Producing a Polyamide-Imide Film]

The process for producing a polyamide-imide film according to anembodiment comprises polymerizing an aromatic diamine compound, anaromatic dianhydride compound, and a dicarbonyl compound to prepare apolyamide-imide polymer solution; charging the polymer solution into atank; extruding and casting the polymer solution in the tank and thendrying the cast polymer solution to prepare a gel sheet; and thermallytreating the gel sheet, wherein the viscosity of the polymer solution is100,000 to 300,000 cps.

In addition, the dicarbonyl compound may comprise a first dicarbonylcompound and a second dicarbonyl compound. In such event, the step ofpreparing a polymer solution may comprise polymerizing an aromaticdiamine compound, an aromatic dianhydride compound, a first dicarbonylcompound, and a second dicarbonyl compound in an organic solvent toobtain a first polymer solution; and further adding the seconddicarbonyl compound to the first polymer solution to obtain a secondpolymer solution, but it is not limited thereto.

Specifically, the process for producing a polyamide-imide film comprisespolymerizing an aromatic diamine compound, an aromatic dianhydridecompound, a first dicarbonyl compound, and a second dicarbonyl compoundin an organic solvent to obtain a first polymer solution; further addingthe second dicarbonyl compound to the first polymer solution to obtain asecond polymer solution having a viscosity of 100,000 to 300,000 cps;charging the second polymer solution into a tank; extruding and castingthe second polymer solution in the tank and then drying the cast secondpolymer solution to prepare a gel sheet; and thermally treating the gelsheet.

The organic solvent employed in the polymerization reaction may be atleast one selected from the group consisting of dimethylformamide (DMF),dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), m-cresol,tetrahydrofuran (THF), and chloroform, but it is not limited thereto.Specifically, the organic solvent employed in the polymerizationreaction may be dimethylacetamide (DMAc), but it is not limited thereto.

The step of obtaining the first polymer solution may comprisesimultaneously or sequentially polymerizing the aromatic diaminecompound, the aromatic dianhydride compound, the first dicarbonylcompound, and the second dicarbonyl compound.

Specifically, in an embodiment, the step of obtaining the first polymersolution may comprise simultaneously polymerizing the aromatic diaminecompound, the aromatic dianhydride compound, the first dicarbonylcompound, and the second dicarbonyl compound.

In another embodiment, the step of obtaining the first polymer solutionmay comprise polymerizing the aromatic diamine compound and the aromaticdianhydride compound to obtain a polyamic acid solution; and adding thefirst dicarbonyl compound and the second dicarbonyl compound to thepolyamic acid solution to polymerize them. The polyamic acid solution isa solution comprising a polyamic acid.

In another embodiment, the step of obtaining the first polymer solutionmay comprise polymerizing the aromatic diamine compound and the aromaticdianhydride compound to obtain a polyamic acid solution; subjecting thepolyamic acid solution to a dehydration reaction to obtain a polyimidesolution; and adding the first dicarbonyl compound and the seconddicarbonyl compound to the polyimide solution to polymerize them. Thepolyimide solution is a solution comprising a polymer having an imiderepeat unit.

In another embodiment, the step of obtaining the first polymer solutionmay comprise polymerizing the aromatic diamine compound, the firstdicarbonyl compound, and the second dicarbonyl compound to obtain anamide polymer solution; and adding the aromatic dianhydride compound tothe amide polymer solution to polymerize them. The amide polymersolution is a solution comprising a polymer having amide repeat units.

The copolymer comprised in the first polymer solution comprises an imiderepeat unit derived from the polymerization of the aromatic diaminecompound and the aromatic dianhydride compound and amide repeat unitsderived from the polymerization of the aromatic diamine compound and thedicarbonyl compound.

A catalyst may be further added in the step of obtaining the firstpolymer solution, in the step of obtaining the second polymer, or afterthe step of obtaining the second polymer.

Examples of the catalyst include, but are not limited to, beta picoline,acetic anhydride, and the like.

The further addition of the catalyst may expedite the reaction rate andproduce the effect of improving the bonding force between the repeatunit structures or that within the repeat unit structure.

In addition, the viscosity of the polymer solution may be appropriatelyadjusted in the steps of adding the catalyst, drying and redissolvingthe polymer solution, or the step of adding the solvent for theextrusion step.

In another embodiment, the step of obtaining the first polymer solutionmay comprise adding the aromatic dianhydride compound, the firstdicarbonyl compound, and the second dicarbonyl compound to an excessiveamount of the aromatic diamine compound.

Specifically, the aromatic dianhydride compound may be employed in anamount of 20% by mole to 50% by mole based on the total moles of thearomatic dianhydride compound, the first dicarbonyl compound, and thesecond dicarbonyl compound, but it is not limited thereto.

If the content of the aromatic dianhydride compound is within the aboverange, the polyamide-imide film has excellent mechanical properties interms of modulus, tensile strength, elongation, surface hardness, andthe like.

In addition, the first dicarbonyl compound and the second dicarbonylcompound may be employed in an amount of 50% by mole to 80% by molebased on the total moles of the aromatic dianhydride compound, the firstdicarbonyl compound, and the second dicarbonyl compound, but it is notlimited thereto.

If the content of the dicarbonyl compounds is within the above range,the polyamide-imide film has excellent optical properties in terms oflight transmittance, haze, and the like.

In the step of obtaining the first polymer solution in anotherembodiment, the first dicarbonyl compound may be employed in an amountof 50% by mole to 70% by mole based on the total moles of the firstdicarbonyl compound and the second dicarbonyl compound, but it is notlimited thereto.

The first dicarbonyl compound may be 1,1′-biphenyl-4,4′-dicarbonyldichloride (BPDC), and the second dicarbonyl compound may beterephthaloyl chloride (TPC).

If the content of the first dicarbonyl compound is less than 50% bymole, such physical properties as tensile strength, modulus, and thelike of the polyamide-imide film may be deteriorated. If the content ofthe first dicarbonyl compound exceeds 70% by mole, such opticalproperties as haze and the like may be deteriorated.

Preferably, in the step of obtaining the first polymer solution, (I) anexcessive amount of the aromatic diamine compound at least in the samemolar amount as that of the other reactants, (II) 20% by mole to 50% bymole of the aromatic dianhydride compound based on the total moles ofthe aromatic dianhydride compound, the first dicarbonyl compound, andthe second dicarbonyl compound, and (III) 50% by mole to 80% of thefirst dicarbonyl compound and the second dicarbonyl compound based onthe total moles of the aromatic dianhydride compound, the firstdicarbonyl compound, and the second dicarbonyl compound may be employed.

Specifically, 50% by mole to 70% of the first dicarbonyl compound (e.g.,1,1′-biphenyl-4,4′-dicarbonyl dichloride, BPDC) and 30% by mole to 50%of the second dicarbonyl compound (e.g., terephthaloyl chloride, TPC)based on the total moles of the first dicarbonyl compound and the seconddicarbonyl compound may be employed.

It is possible to provide a polyamide-imide film whose opticalcharacteristics, mechanical properties, and flexibility are improved ina well-balanced manner without such steps as precipitation, filtration,drying, and redissolution as adopted in the prior art by properlycontrolling the content of the imide repeat unit and those of the amiderepeat units.

After the step of obtaining the first polymer solution, the secondpolymer solution having a viscosity of 100,000 to 300,000 cps may beobtained by further adding the second dicarbonyl compound to the firstpolymer solution.

The weight ratio of the second dicarbonyl compound added in the step ofobtaining the first polymer solution to the second dicarbonyl compoundadded in the step of obtaining the second polymer solution may be 90:10to 99:1, but it is not limited thereto.

In addition, the second dicarbonyl compound added in the step ofobtaining the second polymer solution may be in the form of a solutionin which the second dicarbonyl compound is dissolved in an organicsolvent at a concentration of 5 to 20% by weight, but it is not limitedthereto.

This is advantageous in that the desired viscosity can be accuratelyachieved.

The viscosity of the second polymer solution may be 100,000 to 300,000cps, but it is not limited thereto.

If the viscosity of the second polymer solution is within the aboverange, a polyamide-imide film can be effectively produced in theextrusion and casting steps. In addition, the polyamide-imide film thusproduced may have mechanical properties in terms of an improved modulusand the like.

According to an embodiment, the content of solids contained in thesecond polymer solution may be 10% by weight to 20% by weight.Specifically, the content of solids contained in the second polymersolution may be 12% by weight to 18% by weight, but it is not limitedthereto.

If the content of solids contained in the second polymer solution iswithin the above range, a polyamide-imide film can be effectivelyproduced in the extrusion and casting steps. In addition, thepolyamide-imide film thus produced may have mechanical properties interms of an improved modulus and the like and optical properties interms of a low yellow index and the like.

After the second polymer solution is obtained, the pH of the secondpolymer solution may be adjusted by adding a neutralizing agent.

Examples of the neutralizing agent include, but are not limited to,amine-based neutralizing agents such as alkoxyamine, alkylamine,alkanolamine, and the like.

The neutralizing agent may be employed in an amount of about 0.1% bymole to about 10% by mole based on the total number of moles of monomersin the polyamide-imide polymer solution.

The pH of the second polymer solution adjusted by the neutralizing agentmay be about 4 to about 7. Specifically, the adjusted pH of the secondpolymer solution may be about 4.5 to about 7.

If the pH of the second polymer solution is within the above-describedrange, it is possible to prevent damage to the equipment in thesubsequent extrusion and casting steps. Further, the polyamide-imidefilm thus produced may have an effect in that its optical properties areimproved by, for example, lowering the yellow index or preventingincreases in the yellow index and that its mechanical properties areimproved in terms of modulus and the like.

After the step of obtaining the polymer solution or the step ofobtaining the second polymer solution, the polymer solution is chargedinto a tank.

Here, once the polymer solution is obtained, the step of transferringthe polymer solution to the tank is carried out without any additionalsteps. Specifically, the polymer solution prepared in the polymerizationequipment is transferred to, and stored in, the tank without anyseparate precipitation and redissolution steps in order to removeimpurities. In the conventional process, in order to remove impuritiessuch as hydrochloric acid (HCl) generated during the preparation of apolymer solution, a polymer solution prepared is purified through aseparate step to remove impurities, and the purified polymer solution isthen redissolved in a solvent. In this case, however, there has been aproblem that the loss of the active ingredient increases in the step ofremoving the impurities, resulting in decreases in the yield.

Accordingly, the production process according to the embodimentultimately minimizes the amount of impurities generated in the step ofpreparing a polymer solution or properly controls the impurities in thesubsequent steps, even if a certain amount of impurities is present, soas not to deteriorate the physical properties of the final film. Thus,the process has an advantage in that a film is produced without separateprecipitation or redissolution steps.

Here, the temperature inside the tank is preferably −20 to 0° C. This isto prevent degradation of the charged polymer solution and to lower themoisture content therein.

After the step of charging the prepared polymer solution into the tank,the process may further comprise vacuum degassing for 1 to 2 hours untilthe pressure in the tank is lowered to 0.2 to 0.4 bar.

Alternatively, after the step of charging the prepared polymer solutioninto the tank, the process may further comprise purging the tank withnitrogen gas at 1 to 2 atmospheres.

The step of vacuum degassing and the step of purging the tank withnitrogen gas are performed in a separate process, respectively.

For example, the step of vacuum degassing may be carried out, followedby the step of purging the tank with nitrogen gas, but it is not solimited.

The step of vacuum degassing and/or the step of purging the tank withnitrogen may improve the physical properties of the surface of thepolyamide-imide film thus produced.

Then, the polymer solution in the tank is extruded and cast, followed bydrying the cast polymer solution to prepare a gel sheet.

In the above extrusion and casting steps, the above-mentioned organicsolvent may be used.

The polymer solution is extruded and cast onto a casting body such as acasting roll, a casting belt, and the like. In such event, the polymersolution is cast at a rate of about 0.5 m/min to about 15 m/min and in athickness of 200 to 700 μm onto the casting body. If the extrusion andcasting rates are within the above ranges, the polyamide-imide film thusproduced by the production process according to the embodiment can haveimproved optical characteristics and mechanical characteristics.

That is, if the polymer solution has a viscosity in the above-mentionedrange, the extrusion and casting at the extrusion rate as describedabove may be advantageous to have improved optical characteristics andmechanical characteristics.

After the polymer solution is cast onto a casting body, the solventcontained in the polymer solution is removed by a drying step to therebyform a gel sheet on the casting body.

The drying step may be carried out at a temperature of from about 60° C.to about 150° C. for a period of time ranging from about 5 minutes toabout 60 minutes.

Thereafter, the gel sheet is thermally treated to thereby produce thepolyamide-imide film according to the embodiment.

The thermal treatment may be carried out in a temperature range of 80 to500° C. at a temperature elevation rate of 2° C./min to 80° C./min for 5to 40 minutes or 5 to 30 minutes. Specifically, the thermal treatmentmay be carried out in a temperature range of 80 to 470° C. at atemperature elevation rate of 10° C./min to 80° C./min for 5 to 30minutes or 5 to 20 minutes.

The maximum temperature in the thermal treatment may be 300 to 500° C.or 320 to 500° C. More specifically, the maximum temperature in thethermal treatment may be 350 to 500° C., 380 to 500° C., 400 to 500° C.,410 to 480° C., 410 to 470° C., or 410 to 450° C., but it is not limitedthereto.

After the thermal treatment step, a step of lowering the temperature ofthe thermally treated sheet may be further carried out. The temperaturelowering step may comprise a first temperature lowering step of reducingthe temperature at a rate of 100° C./min to 1,000° C./min and a secondtemperature lowering step of reducing the temperature at a rate of 40°C./min to 400° C./min.

Specifically, the second temperature lowering step is performed afterthe first temperature lowering step.

In addition, the temperature lowering rate of the first temperaturelowering step may be faster than the temperature lowering rate of thesecond temperature lowering step.

For example, the maximum rate of the first temperature lowering step isfaster than the maximum rate of the second temperature lowering step. Orthe minimum rate of the first temperature lowering step is faster thanthe minimum rate of the second temperature lowering steps.

Since the polyamide-imide polymer has high oxidation resistance, it ishardly affected by oxygen contained in the atmosphere during the thermaltreatment step. Thus, the polyamide-imide film according to theembodiment may have improved optical characteristics.

In addition, nitrogen gas purging is carried out when a polyimide filmis formed in the conventional process in order to prevent yellowing ofthe film and to secure transparency of the film. According to theembodiment, however, a polyamide-imide film having excellent opticalcharacteristics can be produced without such nitrogen gas purging.

Details on the polyamide-imide film produced by the process forproducing a polyamide-imide film are referenced to the description givenin the above section of [Polyamide-imide film].

For example, the peak area in the vicinity of 2θ=23° is 50% or morebased on the peak area in the vicinity of 2θ=15° when a base line istaken in the region between 2θ=8° and 32° in an XRD graph of thepolyamide-imide film produced by the above production process.

MODE FOR THE INVENTION

Hereinafter, the present invention will be described in detail byreferring to Examples. But the following Examples are intended tofurther illustrate the present invention, and the scope of the presentinvention is not limited thereto.

Examples 1 to 3

Dimethyl acetamide (DMAc) as an organic solvent was charged in a 1 Lglass reactor equipped with a temperature-controllable double jacketunder a nitrogen atmosphere at 20° C. Then,2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB) as an aromaticdiamine was slowly added thereto for dissolution thereof.

Subsequently, while 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropanedianhydride (6-FDA) as an aromatic dianhydride was slowly added thereto,the mixture was stirred for 1 hour.

Then, 1,1′-biphenyl-4,4′-dicarbonyldichloride (BPDC) as a firstdicarbonyl compound was added, followed by stirring for 1 hour. Andterephthaloyl chloride (TPC) as a second dicarbonyl compound was added,followed by stirring for 1 hour, thereby preparing a first polymersolution.

The viscosity of the first polymer solution thus prepared was measured.If the measured viscosity did not reach the target viscosity, a TPCsolution in a DMAc organic solvent at a concentration of 10% by weightwas prepared, and 1 mL of the TPC solution was added to the firstpolymer solution, followed by stirring for 30 minutes. This procedurewas repeated until the viscosity fell within the range of 100,000 cps to300,000 cps, thereby preparing a second polymer solution.

The second polymer solution was coated onto a glass plate and then driedwith hot air at 80° C. for 30 minutes. The dried polyamide-imide polymerwas peeled off from the glass plate, fixed to a pin frame, and thermallytreated for 30 minutes in a temperature range of 80° C. to 500° C. at atemperature elevation rate of 2° C./min to 80° C./min to obtain apolyamide-imide film having a thickness of 50 m.

According to the above Example, the yield reached about 100% immediatelybefore the film formation step (i.e., immediately before coating). Here,the “yield” refers to the ratio of the number of moles of the materialsremaining in the solution for coating to the number of moles of thecharged materials.

According to the conventional production process, the yield immediatelybefore the film formation step is about 60%, which attributes to theloss of the materials that inevitably takes place at the steps ofpolyimidization, precipitation, filtration, and drying.

In Examples 1 to 3, a polyamide-imide film was each produced in the samemanner as described above, except that the molar ratios of TFDB, 6-FDA,TPC, and BPDC and the maximum temperature during the thermal treatmentstep were as shown in Table 1 below.

Comparative Example 1

Dimethyl acetamide (DMAc) as an organic solvent was charged in a 1 Lglass reactor equipped with a temperature-controllable double jacketunder a nitrogen atmosphere at 20° C. Then,2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB) as an aromaticdiamine was slowly added thereto for dissolution thereof.

Subsequently, while 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropanedianhydride (6-FDA) as an aromatic dianhydride was slowly added thereto,the mixture was stirred for 1 hour.

Then, 1,1′-biphenyl-4,4′-dicarbonyldichloride (BPDC) as a firstdicarbonyl compound was added, followed by stirring for 1 hour. Sebacoyldichloride (SD) as a second dicarbonyl compound was added, followed bystirring for 1 hour. And terephthaloyl chloride (TPC) as a thirddicarbonyl compound was added, followed by stirring for 1 hour, therebypreparing a first polymer solution.

The viscosity of the first polymer solution thus prepared was measured.If the measured viscosity did not reach the target viscosity, a TPCsolution in a DMAc organic solvent at a concentration of 10% by weightwas prepared, and 1 mL of the TPC solution was added to the firstpolymer solution, followed by stirring for 30 minutes. This procedurewas repeated until the viscosity fell within the range of 100,000 cps to300,000 cps, thereby preparing a second polymer solution.

The second polymer solution was coated onto a glass plate and then driedwith hot air at 80° C. for 30 minutes. The dried polyamide-imide polymerwas peeled off from the glass plate, fixed to a pin frame, and thermallytreated for 30 minutes in a temperature range of 80° C. to 500° C. at atemperature elevation rate of 2° C./min to 80° C./min to obtain apolyamide-imide film having a thickness of 50 μm.

Comparative Example 2

Dimethyl acetamide (DMAc) as an organic solvent was charged in a 1 Lglass reactor equipped with a temperature-controllable double jacketunder a nitrogen atmosphere at 20° C. Then,2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB) as an aromaticdiamine was slowly added thereto for dissolution thereof.

Subsequently, while 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropanedianhydride (6-FDA) as an aromatic dianhydride was slowly added thereto,the mixture was stirred for 1 hour, thereby preparing a polymersolution.

The polymer solution was coated onto a glass plate and then dried withhot air at 80° C. for 30 minutes. The dried polyamide-imide polymer waspeeled off from the glass plate, fixed to a pin frame, and thermallytreated for 30 minutes in a temperature range of 80° C. to 500° C. at atemperature elevation rate of 2° C./min to 80° C./min to obtain apolyamide-imide film having a thickness of 50 μm.

TABLE 1 Molar ratio Max. temp. during TFDB 6-FDA TPC BPDC SD thermaltreatment (° C.) Ex. 1 0.200 0.052 0.066 0.082 — 420 Ex. 2 0.200 0.0420.050 0.100 — 420 Ex. 3 0.200 0.052 0.066 0.082 — 300 C. Ex. 1 0.2000.060 0.072 0.040 0.020 420 C. Ex. 2 0.200 0.200 — — — 300

Evaluation Example

The films according to Examples 1 to 3 and Comparative Examples 1 and 2were measured and evaluated for the following properties. The resultsare shown in Table 2 below and FIGS. 1 to 5.

Evaluation Example 1: Measurement of Film Thickness

5 points were measured in the width direction with a Digital Micrometer547-401 manufactured by Mitsutoyo Corporation, Japan, and an averagevalue thereof was taken as a thickness.

Evaluation Example 2: Measurement of Modulus

The compressive strength of a film was measured by a universal testingmachine UTM 5566A of Instron. A sample was cut out by at least 5 cm inthe direction perpendicular to the main shrinkage direction of the filmand by 10 cm in the main shrinkage direction. It was fixed by the clipsdisposed at intervals of 5 cm in the machine. A stress-strain curve wasobtained until the sample was fractured while it was stretched at a rateof 5 mm/min at room temperature. The slope of the load with respect tothe initial strain in the stress-strain curve was taken as a modulus(GPa).

Evaluation Example 3: Measurement of Surface Hardness

The surface hardness was measured with a pencil hardness measuringinstrument (CT-PCl, CORE TECH, Korea) with a pencil hardness measuringpencil mounted at an angle of 45° and at a pencil speed of 300 mm/minwhile a constant load (750 g) was applied. The pencil used wasMitsubishi pencils having a strength of H to 9H, F, HB, B to 6B, and thelike.

Evaluation Example 4: Measurement of Yellow Index (YI)

The yellow Index (YI) was measured with a spectrophotometer (UltraScanPRO, Hunter Associates Laboratory) using a CIE colorimetric system.

Evaluation Example 5: Measurement of Light Transmittance and Haze (HZ)

The light transmittance at 550 nm and the haze were measured using ahaze meter NDH-5000W manufactured by Nippon Denshoku Kogyo.

Evaluation Example 6: XRD Graph

A sample was irradiated with X-ray to measure the diffraction angle (20)of diffracted X-ray using an Ultima IV X-ray diffraction apparatus ofRigaku Corporation, Japan.

The region between 2θ=8° to 32° was taken as a base line in the XRDgraph result thus obtained. The peak area in the vicinity of 2θ=15° andthat in the vicinity of 2θ=23° were each obtained in a Gaussian typeusing the JADE 9 software supplied by MDI.

Next, the peak area in the vicinity of 2θ=23° with respect to the peakarea in the vicinity of 2θ=15° taken as 100% was calculated in percent.

TABLE 2 Peak Peak Thickness Modulus Surface Haze Transmittance area areaXRD (μm) (GPa) hardness YI (%) (%, 550 nm) 2θ = 15° 2θ = 23° graph Ex. 150 5.57 2 H 3.59 0.30 89.1 100 76.6 FIG. 1 Ex. 2 50 6.60 2 H 1.03 0.8889.0 100 83.4 FIG. 2 Ex. 3 50 5.25 2 H 3.99 0.35 88.6 100 60.5 FIG. 3 C.50 3.63 2 H 2.43 0.33 91.4 100 49.9 FIG. 4 Ex. 1 C. 50 4.47 4 B 3.180.77 91.6 100 40.6 FIG. 5 Ex. 2

As shown in the above Table 2, it was confirmed that the peak area inthe vicinity of 2θ=23° was 50% or more based on the peak area in thevicinity of 2θ=15° when a base line is taken in the region between 2θ=8°and 32° in an XRD graph of the polyamide-imide film in Examples 1 to 3,unlike Comparative Examples 1 and 2. Such specific XRD characteristicssecure an excellent level of such characteristics as modulus, surfacehardness, yellow index, haze, transmittance, and the like.

1. A polyamide-imide film, which comprises a polyamide-imide polymer formed by polymerizing an aromatic diamine compound, an aromatic dianhydride compound, and a dicarbonyl compound, wherein the peak area in the vicinity of 2θ=23° is 50% or more based on the peak area in the vicinity of 2θ=15° when a base line is taken in the region between 2θ=8° and 32° in an XRD graph of the polyamide-imide film.
 2. The polyamide-imide film of claim 1, wherein the peak area in the vicinity of 2θ=23° is 60% or more based on the peak area in the vicinity of 2θ=15° when a base line is taken in the region between 2θ=8° and 32° in an XRD graph of the polyamide-imide film.
 3. The polyamide-imide film of claim 1, which has a modulus of 5.0 GPa or more based on a thickness of 50 μm.
 4. The polyamide-imide film of claim 1, which has a surface hardness of HB or higher.
 5. The polyamide-imide film of claim 1, which has a yellow index (YI) of 5 or less based on a thickness of 50 μm.
 6. The polyamide-imide film of claim 1, which has a haze of 2% or less based on a thickness of 50 μm.
 7. The polyamide-imide film of claim 1, which has a light transmittance measured at 550 nm of 85% or more based on a thickness of 50 μm.
 8. The polyamide-imide film of claim 1, wherein the aromatic dianhydride compound is composed of a compound having a fluorine-containing substituent.
 9. The polyamide-imide film of claim 1, wherein the aromatic diamine compound comprises 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB), and the aromatic dianhydride compound comprises 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA).
 10. The polyamide-imide film of claim 1, wherein the molar ratio of the aromatic diamine compound to the aromatic dianhydride compound is 10:2 to 10:4.
 11. The polyamide-imide film of claim 1, wherein the dicarbonyl compound comprises at least two dicarbonyl compounds different from each other.
 12. The polyamide-imide film of claim 1, wherein the dicarbonyl compound comprises terephthaloyl chloride (TPC), 1,1′-biphenyl-4,4′-dicarbonyl dichloride (BPDC), or a combination thereof.
 13. A process for producing a polyamide-imide film, which comprises polymerizing an aromatic diamine compound, an aromatic dianhydride compound, and a dicarbonyl compound to prepare a polyamide-imide polymer solution; charging the polymer solution into a tank; extruding and casting the polymer solution in the tank and then drying the cast polymer solution to prepare a gel sheet; and thermally treating the gel sheet, wherein the viscosity of the polymer solution is 100,000 to 300,000 cps, the thermal treatment is carried out in a temperature range of 80 to 500° C. at a temperature elevation rate of 2° C./min to 80° C./min for 5 to 40 minutes, and the maximum temperature in the thermal treatment is 300 to 500° C.
 14. The process for producing a polyamide-imide film of claim 13, wherein the temperature inside the tank is −20 to 0° C.
 15. The process for producing a polyamide-imide film of claim 13, which further comprises vacuum degassing for 1 to 2 hours until the pressure in the tank is lowered to 0.2 to 0.4 bar after the step of charging the prepared polymer solution into the tank.
 16. The process for producing a polyamide-imide film of claim 13, which further comprises purging the tank with nitrogen gas at 1 to 2 atmospheres after the step of charging the prepared polymer solution into the tank.
 17. The process for producing a polyamide-imide film of claim 13, wherein the drying is carried out at a temperature of 60° C. to 150° C. for a period of time ranging from 5 minutes to 60 minutes.
 18. The process for producing a polyamide-imide film of claim 13, wherein the maximum temperature in the thermal treatment is 400 to 500° C.
 19. The process for producing a polyamide-imide film of claim 13, which further comprises lowering the temperature of the thermally treated sheet after the thermal treatment step, wherein the temperature lowering step comprises a first temperature lowering step of reducing the temperature at a rate of 100° C./min to 1,000° C./min and a second temperature lowering step of reducing the temperature at a rate of 40° C./min to 400° C./min; the second temperature lowering step is performed after the first temperature lowering step; and the temperature lowering rate of the first temperature lowering step is faster than the temperature lowering rate of the second temperature lowering step.
 20. The process for producing a polyamide-imide film of claim 13, wherein the peak area in the vicinity of 2θ=23° is 50% or more based on the peak area in the vicinity of 2θ=15° when a base line is taken in the region between 2θ=8° and 32° in an XRD graph of the polyamide-imide film. 